CN109030595B - Biosensor electrode and biosensor - Google Patents
Biosensor electrode and biosensor Download PDFInfo
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- CN109030595B CN109030595B CN201710434460.9A CN201710434460A CN109030595B CN 109030595 B CN109030595 B CN 109030595B CN 201710434460 A CN201710434460 A CN 201710434460A CN 109030595 B CN109030595 B CN 109030595B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3271—Amperometric enzyme electrodes for analytes in body fluids, e.g. glucose in blood
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
Abstract
The invention relates to a biosensor electrode, which comprises a porous metal composite structure, wherein the porous metal composite structure comprises a porous metal structure and a carbon nano tube structure, the carbon nano tube structure is fixed on the surface of the porous metal structure, the carbon nano tube structure comprises a plurality of carbon nano tubes, and the porous metal composite structure comprises a plurality of folds. The invention further relates to a biosensor.
Description
Technical Field
The present invention relates to a biosensor electrode and a biosensor.
Background
The biosensor is used for detecting the concentration of biomolecules, and has the characteristics of high sensitivity, good reliability, quick response, good selectivity and low cost. The biosensor is composed of a molecular recognition element that recognizes a biochemical reaction signal and a signal conversion element for converting the biochemical reaction signal into an electrical signal. The molecular recognition element in a biosensor is generally composed of an electrode for collecting an electric current generated by a biochemical reaction and a material having an electrocatalytic property for performing a biochemical reaction with a biomolecule to be measured for catalysis, which is generally combined with the electrode by bonding or physical contact.
At present, the electrode material is generally nano porous metal, and the nano porous metal has larger specific surface area, so that higher sensitivity and lower detection limit are realized. However, as shown in fig. 1, the crimped nano-porous metal has a phenomenon of incomplete ligament connection, so that the crimped nano-porous metal has low mechanical strength and poor toughness and is easy to fracture, thereby affecting the service lives of the biosensor electrode and the biosensor.
Disclosure of Invention
In view of this, it is indeed necessary to provide a biosensor electrode and a biosensor that have a long service life.
The biosensor electrode comprises a porous metal composite structure, wherein the porous metal composite structure comprises a porous metal structure and a carbon nanotube structure, the carbon nanotube structure is fixed on the surface of the porous metal structure, the carbon nanotube structure comprises a plurality of carbon nanotubes, and the porous metal composite structure comprises a plurality of folds.
The biosensor comprises a molecular recognition element and a signal conversion element, wherein the molecular recognition element is used for recognizing biochemical reaction signals generated after a biomolecule to be detected is catalyzed, the signal conversion element is used for converting the biochemical reaction signals recognized by the molecular recognition element into electrochemical signals, the molecular recognition element comprises a porous metal composite structure, the porous metal composite structure comprises a porous metal structure and a carbon nano tube structure, the carbon nano tube structure is fixed on the surface of the porous metal structure, the carbon nano tube structure comprises a plurality of carbon nano tubes, and the porous metal composite structure comprises a plurality of folds.
Compared with the prior art, the carbon nano tube in the biosensor electrode and the biosensor provided by the invention is fixed on the surface of the porous metal structure, and the porous metal composite structure is not easy to break due to the good mechanical strength and toughness of the carbon nano tube, so that the toughness of the biosensor electrode and the biosensor is improved, and the service lives of the biosensor electrode and the biosensor are prolonged.
Drawings
FIG. 1 is a scanning electron microscope image of a prior art pleated nanoporous gold film at high magnification.
FIG. 2 shows an embodiment of the present invention formed with MnO 2 Under high power lensScanning electron microscope images.
FIG. 3 is a scanning electron microscope image of a porous metal composite structure provided by an embodiment of the invention under a low power mirror.
Fig. 4 is a scanning electron microscope image of the porous metal composite structure provided by the embodiment of the invention under a high power mirror.
Fig. 5 is a scanning electron microscope image of a porous metal composite structure provided by an embodiment of the present invention.
Fig. 6 is a schematic structural view of the fold portion in fig. 5 according to an embodiment of the present invention.
Fig. 7 is a schematic flow chart of a method for preparing a porous metal composite structure according to an embodiment of the present invention.
FIG. 8 is a scanning electron microscope characterization of a nanoporous gold film in a porous metal composite structure provided by an embodiment of the invention.
Fig. 9 is a scanning electron microscope characterization diagram of a second composite structure in the porous metal composite structure provided by the embodiment of the invention.
Fig. 10 is a scanning electron microscope image of a second composite structure in the porous metal composite structure according to the embodiment of the present invention.
Detailed Description
The biosensor electrode and the biosensor provided by the invention will be described in further detail below with reference to the accompanying drawings and specific examples.
The invention provides a biosensor electrode, which comprises a porous metal composite structure, wherein the porous metal composite structure comprises a porous metal structure and a carbon nano tube structure, the carbon nano tube structure is fixed on the surface of the porous metal structure, the carbon nano tube structure comprises a plurality of carbon nano tubes, and the porous metal composite structure comprises a plurality of folds.
The biosensor electrode may be composed of only a porous metal composite structure, which has both conductivity and catalytic properties, and can collect electrons and perform catalytic reactions simultaneously, because the carbon nanotube structure has good mechanical strength, toughness, and conductivity on the one hand, and the porous metal structure and the carbon nanotube structure have good catalytic properties on the other hand.
Referring to fig. 2, the biosensor electrode may further include a catalytic material disposed on a surface of the porous metal composite structure. Further, the catalytic material is located on gaps between adjacent carbon nanotubes in the carbon nanotube structure and on the ductile band of the porous metal structure. The catalytic material is integrated with the porous metal structure, no additive is required to be introduced, the internal resistance of the electrode is reduced, and the conductivity of the biosensor electrode is improved.
The catalytic material can be metal oxide, metal and the like, and can further improve the catalytic performance of the biosensor electrode. The metal oxide may be Co 3 O 4 、MnO 2 、TiO 2 And the like, and the shape of the metal oxide can be nano particles, nano sheets, nano flowers and the like. The electrode may be a positive electrode or a negative electrode. In this example, a porous metal composite material was placed in a KMnO-containing material 4 And hydrazine hydrate in aqueous solution, KMnO 4 Is reduced to form MnO 2 Particles, mnO 2 The particles are formed on the surface of the carbon nanotube structure, the gaps between adjacent carbon nanotubes in the carbon nanotube structure, and the ductile bands of the porous metal structure.
Referring to fig. 3 and 4, the porous metal composite structure includes a porous metal structure and a carbon nanotube structure, the carbon nanotube structure is fixed on a surface of the porous metal structure, the carbon nanotube structure includes a plurality of carbon nanotubes, and the porous metal composite structure includes a plurality of folds.
The porous metal structure can be any structure such as a porous metal film, a porous metal nano sheet and the like. The porous metal structure is in a three-dimensional net shape, the porous metal structure comprises a plurality of ligaments, a plurality of holes are formed among the ligaments, and the holes can be distributed regularly, such as in a three-dimensional bicontinuous network form or irregularly. The ligament is made of any one of gold, silver and platinum. The plurality of pores have a pore size on the order of nanometers, preferably the plurality of pores have a pore size of less than 1000nm.
The carbon nanotube structure may be fixed to the surface of the porous metal structure by a connecting material. Specifically, the carbon nanotubes in the carbon nanotube structure are contacted with the ligament in the porous metal structure to form a plurality of contact surfaces, and connecting materials are arranged around the contact surfaces, so that the carbon nanotube structure is not easy to separate from the surface of the porous metal structure. Preferably, the connecting material encloses the contact surface. The connecting material may be an organic adhesive material or a metallic material. The organic bonding material may be a material having a bonding effect such as naphthol, and the metal material may be Au, ag, cu, or the like. Preferably, the metal material is the same as the material of the porous metal structure, so that contact resistance between the metal material and ligaments in the porous metal structure is reduced.
Referring to fig. 5 and 6, the plurality of folds 100 are connected to each other to form a continuous structure. The corrugated portion 100 is formed by bending a porous metal structure 110 and a carbon nanotube structure 120 together. This can also be seen from the above-mentioned figure 3. At the fold portion 100, the carbon nanotubes at the fold of the carbon nanotube structure 120 may extend in the same direction. Specifically, the carbon nanotubes are connected end to end by van der waals force and are arranged along the same direction. It is understood that the arrangement direction of the carbon nanotube structures is not limited.
The fold is irreversibly deformed. Because the carbon nano tube has good toughness, the carbon nano tube transversely penetrates through the fold part to play a role in reinforcing the fold part, the porous metal composite structure formed by fixing the carbon nano tube structure and the porous metal structure has good toughness, the fold part is not easy to break, and the porous metal composite structure has self-supporting performance.
Referring to fig. 7, an embodiment of the present invention further provides a method for preparing a porous metal composite structure, which includes the following steps:
step S20, providing a substrate;
the material of the substrate is selected to be heat shrinkable. Preferably, the substrate is a plastic plate, and the material of the plastic plate is polystyrene, polypropylene, polyethylene terephthalate, and the like. In this embodiment, the material of the plastic plate is polystyrene.
Step S30, fixing a porous metal structure on the surface of the substrate to form a first composite structure;
the fixing method is not limited, and in a certain embodiment, the substrate may be slightly melted by heating the substrate to adhere the porous metal structure, preferably, the substrate and the porous metal structure are heated at a temperature of 80 ℃ for 30 to 60 minutes; in a further embodiment, the first composite structure is transferred to a metal layer comprising Au by growing a metal around the contact surface of the substrate and the porous metal structure + 、Ag + 、Cu + And adding a reducing agent into the solution containing metal ions to form metal particles, wherein the metal particles are deposited around the contact part of ligaments in the porous metal structure and carbon nano tubes in the carbon nano tube structure in an electroless plating mode, so that the porous metal structure is fixed on the surface of the substrate. In this embodiment, the substrate and the porous metal structure are heated at 80 ℃ for 30min, and the surface of the substrate slightly melts during the heating process, and the porous metal structure is bonded on the surface of the substrate.
The method for obtaining the porous metal structure is not limited, and can be various porous metals sold in the current market, and can also be prepared by self. In this embodiment, the porous metal structure is a nano porous gold film, and the nano porous gold film is prepared by a chemical etching method, and the specific method is as follows:
s31, providing an Au-Ag alloy film.
The Au-Ag alloy film is a film material with a smooth surface, has silvery white luster, and has a thickness range of 50nm-200nm. The size of the Au-Ag alloy film is not limited and can be arbitrarily selected according to the needs. In this embodiment, the thickness of the au—ag alloy film is 100nm, the percentage of gold atoms in the au—ag alloy film is 35%, and the percentage of silver atoms is 65%.
S32, placing the Au-Ag alloy film in a concentrated nitric acid solution until the Au-Ag alloy film turns from silvery white to brownish red, so as to form the nano porous gold film.
The concentration range of the concentrated nitric acid can be 50% -80%. The au—ag alloy thin film was transferred to the concentrated nitric acid solution by electrostatic adsorption of the glass sheet. In this embodiment, the concentration of the concentrated nitric acid is 70%. And (3) reacting the Ag in the Au-Ag alloy with the concentrated nitric acid, and forming a plurality of irregular holes on the surface of the Au-Ag alloy film when the Au-Ag alloy film becomes brownish red after the Ag reacts with the concentrated nitric acid completely, so as to form the nano porous gold film.
Referring to fig. 8, the nano-porous gold film has a plurality of pores connected by ligaments, and the pore diameter and ligament size of the plurality of pores are related to factors such as the corrosion time of the au—ag alloy film, the concentration of concentrated nitric acid, and the like.
And S33, placing the nano-porous gold film in deionized water for cleaning.
And transferring the formed nano porous gold film into deionized water by adopting a glass sheet, soaking and cleaning, and continuously replacing the deionized water in the soaking process to thoroughly clean the nitric acid remained on the ligament of the nano porous gold film.
Step S40, fixing a carbon nano tube structure on the surface of the porous metal structure in the first composite structure to form a second composite structure;
referring to fig. 9 and 10, the carbon nanotube structure may be mechanically tiled on the surface of the porous metal structure, and the carbon nanotube structure may be a linear structure, such as a carbon nanotube wire, or may be a carbon nanotube film structure.
The carbon nano-tube lines can be one or more, when the carbon nano-tube lines are a plurality of carbon nano-tube lines, the plurality of carbon nano-tube lines can be arranged in a bundle-shaped structure side by side, can also be arranged in a net-shaped structure in a crossing way, or are twisted with each other to form a twisted wire structure which is intertwined with each other.
The carbon nanotube wire may be a non-twisted carbon nanotube wire or a twisted carbon nanotube wire.
The non-twisted carbon nanotube wire includes a plurality of carbon nanotubes aligned along a length direction of the non-twisted carbon nanotube wire, the plurality of carbon nanotubes are substantially parallel to each other, and an axial direction of the carbon nanotubes is substantially parallel to the length direction of the carbon nanotube wire. Specifically, adjacent carbon nanotubes in the non-twisted carbon nanotube wire line along the axial direction of the non-twisted carbon nanotube wire are connected end to end by van der waals forces. The length of the non-twisted carbon nano-tube line is not limited, and the diameter is 0.5 nanometer to 100 micrometers. Further, the non-twisted carbon nanotube wire may be treated with an organic solvent.
The twisted carbon nanotube wire includes a plurality of carbon nanotubes spirally arranged around an axial direction of the twisted carbon nanotube wire. The twisted carbon nano-tube line can be obtained by twisting two ends of the non-twisted carbon nano-tube line in opposite directions by using a mechanical force.
The twisted carbon nano-tube line and the untwisted carbon nano-tube line are tightly combined with each other by Van der Waals force, so that the twisted carbon nano-tube line and the untwisted carbon nano-tube line have self-supporting structures. The self-support is that the carbon nano-tube line does not need a large-area carrier support, but can be suspended integrally to maintain the self-linear state as long as the supporting force is provided on the opposite sides, namely, when the carbon nano-tube line is placed (or fixed) on two supporting bodies arranged at a certain distance, the carbon nano-tube line between the two supporting bodies can be suspended to maintain the self-linear state.
The carbon nanotube membranous structure can be any membranous structure of a carbon nanotube pulling film, a carbon nanotube flocculation film or a carbon nanotube rolling film. A combination of two or more membranous structures. When the carbon nanotube membranous structure is more than two membranous structures, the more than two membranous structures can be arranged in a coplanar mode or in a laminated mode, and when the more than two membranous structures are in the laminated mode, an included angle between carbon nanotubes in two adjacent layers of carbon nanotube membranous structures can be more than or equal to 0 degree and less than or equal to 90 degrees.
The carbon nanotube film may be one or more layers, and when the carbon nanotube film is a plurality of layers, the plurality of layers of carbon nanotube film may be arranged in a coplanar manner or in a stacked manner. In this embodiment, the carbon nanotube structure is a carbon nanotube pulling film, and since the carbon nanotubes in the carbon nanotube pulling film are connected end to end by van der waals force and extend in the same direction, the internal impedance of the porous metal composite structure can be reduced, and the conductivity of the porous metal composite structure can be improved.
The carbon nanotube tensile film is a self-supporting structure composed of a plurality of carbon nanotubes. The carbon nanotubes are arranged along the same direction, and the preferred orientation arrangement means that the whole extending direction of most carbon nanotubes in the carbon nanotube pulling film is basically towards the same direction. Moreover, the overall extension direction of the majority of the carbon nanotubes is substantially parallel to the surface of the carbon nanotube tensile film. Further, most of the carbon nanotubes in the carbon nanotube pulling film are connected end to end by van der waals forces. Specifically, each of the plurality of carbon nanotubes extending in substantially the same direction in the carbon nanotube tensile film is connected end to end with the carbon nanotube adjacent in the extending direction by van der waals force. Of course, there are a few randomly arranged carbon nanotubes in the carbon nanotube tensile film, which do not significantly affect the overall orientation arrangement of most of the carbon nanotubes in the carbon nanotube tensile film.
The carbon nanotube rolling film can be one or more layers, and when the carbon nanotube rolling film is a plurality of layers, the carbon nanotube rolling film can be arranged in a coplanar mode or a laminated mode.
The carbon nano tube rolling film comprises uniformly distributed carbon nano tubes, wherein the carbon nano tubes are disordered and are arranged in a preferred orientation along the same direction or different directions. Preferably, the carbon nanotubes in the carbon nanotube rolling film extend in substantially the same direction and are parallel to the surface of the carbon nanotube rolling film. The carbon nanotubes in the carbon nanotube rolling film are overlapped with each other, so that the surface of the carbon nanotube rolling film is rough. The carbon nanotubes in the carbon nanotube rolling film are mutually attracted by Van der Waals force to form a plurality of gaps. The carbon nano tube rolling film has good flexibility and can be bent and folded into any shape without cracking. The carbon nanotube flocculent film may be one or more layers, and when the carbon nanotube flocculent film is a plurality of layers, the plurality of layers of carbon nanotube flocculent films may be arranged in a coplanar or laminated manner.
The carbon nanotube flocculating film comprises carbon nanotubes which are intertwined. The carbon nanotubes are mutually attracted and wound through Van der Waals force to form a net structure, so that the surface of the carbon nanotube flocculation film is rough. The carbon nanotubes in the carbon nanotube flocculation film are uniformly distributed and randomly arranged.
The method for fixing the carbon nano tube structure comprises two methods: (one) fixing by an organic adhesive material: dripping an organic bonding material on the surface of the carbon nano tube structure in the first composite structure, wherein the organic bonding material enters the porous metal structure through a gap in the carbon nano tube, and the organic bonding material wraps the contact surface of the porous metal structure and the carbon nano tube structure; (II) fixing by a metal material: transferring the second composite structure to a substrate containing Au + 、Ag + 、Cu + And adding a reducing agent into the solution containing metal ions to form metal particles, wherein the metal particles are deposited around the contact part of ligaments in the porous metal structure and carbon nano tubes in the carbon nano tube structure in an electroless plating mode, so that the porous metal structure and the carbon nano tube structure are combined together. In this embodiment, the first complex structure is transferred to a substrate containing Au + In the solution, hydrazine hydrate is adopted for Au + And (3) reducing to generate Au, wherein the generated Au wraps the periphery of the contact surface of the ligament and the carbon nano tube.
And S50, shrinking the second composite structure to form a porous metal composite structure.
The method for shrinking the second composite structure is not limited as long as the second composite structure formed by the substrate, the porous metal structure and the carbon nanotube structure can be folded. In this embodiment, the second composite structure is heated at 160 ℃ for 2min, the substrate is shrunk, and since the porous metal structure is fixed on the surface of the substrate and the carbon nanotube structure is fixed on the surface of the porous metal structure, the porous metal structure and the carbon nanotube film are driven to shrink together in the process of shrinking the substrate, and at this time, the porous metal structure is not easy to break, and the formed porous composite structure has good toughness.
The porous metal composite structure and the preparation method thereof provided by the embodiment of the invention have the following advantages: firstly, the carbon nano tube has good toughness, so that the toughness of the porous metal composite structure is improved, and the porous metal composite structure is not easy to be brittle broken; secondly, the carbon nano tube has good conductivity, so that the conductivity of the porous metal composite structure is improved.
The invention further provides a biosensor, which comprises a molecular recognition element and a signal conversion element, wherein the signal conversion element converts a biochemical reaction signal recognized by the molecular recognition element into an electrochemical signal, the molecular recognition element comprises a porous metal composite structure, the porous metal composite structure comprises a porous metal structure and a carbon nano tube structure, the carbon nano tube structure is fixed on the surface of the porous metal structure, the carbon nano tube structure comprises a plurality of carbon nano tubes, and the porous metal composite structure comprises a plurality of folds.
The porous metal composite structure reacts with the biomolecule to be detected, the molecular recognition element is used for recognizing a biochemical reaction signal generated after the biomolecule to be detected is catalyzed, and the catalyst in the molecular recognition element reacts with the biomolecule to be detected. The biological molecule to be detected can be glucose molecule, organic molecule, enzyme substrate, antibody or antigen, etc. In this embodiment, the biomolecule to be measured is glucose.
The porous metal composite structure is contacted with the biomolecule to be detected, the biomolecule to be detected is catalyzed under a certain voltage to generate a biochemical reaction signal, the signal conversion element converts the biochemical reaction signal into a physical signal and outputs the physical signal to a signal processing system, and the concentration of the biomolecule to be detected is monitored by processing the physical signal. The porous metal structure and the carbon nano tube structure in the porous metal composite structure have good catalytic performance, and the porous metal structure and the carbon nano tube structure have good conductivity, so that the porous metal composite material can be used for collecting electrons and catalyzing simultaneously, has a simple structure, and reduces the internal resistance of the molecular recognition element.
The molecular recognition element may further include a catalytic material disposed on the surface of the porous metal composite structure, and the catalytic material may be a metal oxide, a metal, or the like, which may further improve catalytic performance of the molecular recognition element. The nano-oxide may be grown on the surface of the porous metal composite structure by a chemical or electrochemical method. The metal oxide may be Co 3 O 4 、 MnO 2 And the like, and the shape of the metal oxide can be nano particles, nano sheets, nano flowers and the like.
The signal conversion element can be a physical or chemical transducer, and the transducer can be any one of an oxygen electrode, a photosensitive tube, a field effect tube, a piezoelectric crystal and the like, and converts a biochemical reaction signal identified by the molecular identification element into a measurable electrochemical signal so as to obtain the concentration of the biological molecule to be detected.
The biosensor electrode and the biosensor provided by the embodiment of the invention have the following advantages: firstly, the carbon nano tube structure is fixed on the surface of the porous metal structure, and the porous metal composite structure has good mechanical strength, toughness and conductivity, so that the toughness, mechanical strength and conductivity of the biosensor electrode and the biosensor are improved, and the service lives of the biosensor electrode and the biosensor are prolonged; secondly, the porous metal structure and the carbon nano tube structure have good catalytic performance, the biosensor electrode can collect electrons and catalyze at the same time, no additional catalytic material is needed to be introduced, and the structure is simple and convenient; thirdly, a catalytic material is formed on the surface of the porous metal composite structure, so that the internal resistance of the biosensor electrode is reduced, and the conductivity of the biosensor electrode and the biosensor is further improved.
Further, other variations within the spirit of the present invention will occur to those skilled in the art, and it is intended, of course, that such variations be included within the scope of the invention as claimed herein.
Claims (8)
1. The biosensor electrode comprises a porous metal composite structure, wherein the porous metal composite structure comprises a porous metal structure and a carbon nano tube structure, the carbon nano tube structure is fixed on the surface of the porous metal structure, the carbon nano tube structure comprises a plurality of carbon nano tubes, the porous metal composite structure comprises a plurality of fold parts, the fold parts are formed by bending the porous metal structure and the carbon nano tube structure together, the plurality of carbon nano tubes are connected end to end on the surface of the porous metal structure through van der Waals force and extend and arrange along the same direction, the porous metal structure comprises a plurality of ligaments, a plurality of holes are formed among the ligaments, and the outer surfaces of the plurality of carbon nano tubes are in direct contact with the ligaments of the porous metal structure.
2. The biosensor electrode of claim 1, further comprising a catalytic material disposed on a surface of said porous metal composite structure.
3. The biosensor electrode of claim 1, wherein said plurality of folds are interconnected to form a continuous structure.
4. The biosensor electrode of claim 1, wherein said porous metal composite structure further comprises a connecting material for fixing the carbon nanotube structure to the surface of said porous metal structure.
5. The biosensor electrode according to claim 4, wherein said connecting material encapsulates the contact surface formed by said porous metal structure and carbon nanotube structure.
6. The biosensor electrode according to claim 4, wherein said connecting material is an organic adhesive material or a metallic material.
7. The biosensor electrode of claim 1, wherein said biosensor electrode is comprised of said porous metal structure and said carbon nanotube structure.
8. A biosensor comprising a molecular recognition element for recognizing a biochemical reaction signal generated after a biomolecule to be detected is catalyzed, and a signal conversion element for converting the biochemical reaction signal recognized by the molecular recognition element into an electrochemical signal, the molecular recognition element being the biosensor electrode according to any one of claims 1 to 7.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710434460.9A CN109030595B (en) | 2017-06-09 | 2017-06-09 | Biosensor electrode and biosensor |
| TW106121383A TWI671525B (en) | 2017-06-09 | 2017-06-27 | Biosensor electrode and biosensor using the same |
| US15/798,795 US10942143B2 (en) | 2017-06-09 | 2017-10-31 | Biosensor electrode and biosensor using the same |
| JP2018110606A JP6532987B2 (en) | 2017-06-09 | 2018-06-08 | Biological sensor electrode and biological sensor |
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| CN201710434460.9A CN109030595B (en) | 2017-06-09 | 2017-06-09 | Biosensor electrode and biosensor |
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| CN109030595B true CN109030595B (en) | 2023-09-26 |
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| CN111208180B (en) * | 2020-01-14 | 2021-11-23 | 山东大学 | Method for improving bioelectrode construction by using reduced graphene oxide nano material |
| GB2613332A (en) * | 2021-10-26 | 2023-06-07 | H2D20 Ltd | Memrane-less electrolyser cell utilising carbon nanotubes |
| CN114894867B (en) * | 2022-03-25 | 2023-04-07 | 江南大学 | Hydrogen peroxide electrochemical detection method based on Au-Ag @ manganese dioxide nano material |
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| CN109030595A (en) | 2018-12-18 |
| TWI671525B (en) | 2019-09-11 |
| JP2019002922A (en) | 2019-01-10 |
| US10942143B2 (en) | 2021-03-09 |
| TW201903403A (en) | 2019-01-16 |
| JP6532987B2 (en) | 2019-06-19 |
| US20180356361A1 (en) | 2018-12-13 |
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